Interfacing anisotropic gold nanostructures with graphene can open up new avenues for modifying the light–matter interaction of graphene. A chemical route is explored to synthesize branched gold nanostructures on reduced graphene oxide (rGO) layers by in situ reduction, assisted by binary surfactant mixtures containing tetraoctylammonium bromide with cetyltrimethy­lammonium bromide, sodium dodecylsulfate, or sodium citrate. The hybrid material self-assembles at a liquid/liquid interface forming a free-standing film. Electron microscopy studies reveal the morphology, microstructure, and crystallinity of the hybrids. The gold nanostructures are branched in three dimensions and possess various shapes, such as irregular stars, multipods, and spiky features, interspersed with rGO layers. The hybrids exhibit plasmon modes in the visible and near-infrared region due to the shape anisotropy. The enhancement effect of the spiky features is also observed in the Raman spectra. The growth mechanism of the branched nanostructures is followed by kinetic studies and indicates that the formation of multiple twinned crystals is the key factor for branching.